EP3519457A1 - Verfahren zur herstellung eines prokatalysators zur polymerisierung von olefinen - Google Patents

Verfahren zur herstellung eines prokatalysators zur polymerisierung von olefinen

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Publication number
EP3519457A1
EP3519457A1 EP17730197.5A EP17730197A EP3519457A1 EP 3519457 A1 EP3519457 A1 EP 3519457A1 EP 17730197 A EP17730197 A EP 17730197A EP 3519457 A1 EP3519457 A1 EP 3519457A1
Authority
EP
European Patent Office
Prior art keywords
compound
stage
procatalyst
added
minutes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17730197.5A
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English (en)
French (fr)
Inventor
Akhlaq Moman
Inaamul Haq SIDDIQUI
Sudhakar R. PADMANABHAN
Osamah AL-HUMAIDAN
Haitham AL-ENAZI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
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SABIC Global Technologies BV
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Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Priority claimed from PCT/EP2017/064951 external-priority patent/WO2018059750A1/en
Publication of EP3519457A1 publication Critical patent/EP3519457A1/de
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/651Pretreating with non-metals or metal-free compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04Monomers containing three or four carbon atoms
    • C08F210/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652Pretreating with metals or metal-containing compounds
    • C08F4/656Pretreating with metals or metal-containing compounds with silicon or compounds thereof
    • C08F4/6565Pretreating with metals or metal-containing compounds with silicon or compounds thereof and magnesium or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06Catalyst characterized by its size

Definitions

  • the invention relates to a process to prepare a procatalyst for polymerization of olefins comprising an activator and an internal donor.
  • the invention also relates to said procatalyst obtained.
  • the invention is directed to a catalyst system for polymerization of olefins comprising said procatalyst, optionally a co-catalyst and optionally an external electron donor.
  • the invention is related to a process of making polyolefins by contacting at least one olefin with said catalyst system.
  • the present invention relates to polymers obtained by polymerization using said procatalyst and to the shaped articles of said polymers.
  • Catalyst systems and their components that are suitable for preparing a polyolefin are generally known.
  • One type of such catalysts is generally referred to as Ziegler-Natta catalysts.
  • the term "Ziegler-Natta” is known in the art and it typically refers to catalyst systems comprising an organometallic compound (also typically referred to as a co- catalyst) and optionally one or more electron donor compounds (e.g. external electron donors) and a transition metal-containing solid catalyst compound (also typically referred to as a procatalyst), comprising a transition metal halide (e.g.
  • a metal or metalloid compound e.g. a magnesium compound or a silica compound.
  • the present invention relates to a process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, said process comprising the steps of: Step A) providing or preparing a Grignard compound; Step B) contacting the Grignard compound an alkoxy- or aryloxy silane compound, to give a solid support; Step C) optionally contacting the solid support obtained with at least one activating compound; and Step D) reacting the (activated) support with a halogen-containing Ti-compound as catalytic species, an activator and at least one internal electron donor in several sub steps wherein the internal donor is added in portions during at least two of said stages to obtain a procatalyst.
  • a first aspect of the present invention is a process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, said process comprising the steps as disclosed in claim 1.
  • This process involves the split addition of the internal donor.
  • a second aspect of the present invention is shown in claim 10. This process involves a decreased temperature during the addition of the activator and optionally internal donor and/or involves an increased mixing time during titanation stages I and/or II of step D for preparing the procatalyst.
  • a third aspect of the present invention is a procatalyst obtained or obtainable or directly obtainable by the process according to the invention.
  • a fourth aspect of the present invention is a process for the preparation of polyolefins, preferably polypropylene, comprising the contacting of a procatalyst with an olefin, and optionally an external donor and/or optionally a co-catalyst or contacting a catalyst system - comprising a procatalyst, an external donor and a co-catalyst, with an olefin.
  • a fifth aspect of the present invention is a polyolefin, preferably a polypropylene, obtainable or directly obtainable by said process.
  • a sixth aspect of the present invention is a shaped article of said polyolefin.
  • Zeroegler-Natta catalyst as used in the present description means: a transition metal- containing solid catalyst compound comprises catalytic species supported on a metal or metalloid compound (e.g. a magnesium compound or a silica compound),
  • a metal or metalloid compound e.g. a magnesium compound or a silica compound
  • a transition metal-containing species comprises a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide and vanadium halide.
  • internal donor or "internal electron donor” or “ID” as used in the present description means: an electron-donating compound containing one or more atoms of oxygen (O) and/or nitrogen (N).
  • external donor or “external electron donor” or “ED” as used in the present description means: an electron-donating compound used as a reactant in the polymerisation of olefins. It comprises at least one functional group that is capable of donating at least one pair of electrons to a metal atom.
  • activator as used in the present description means: an electron-donating compound containing one or more atoms of oxygen (O) and/or nitrogen (N) which is used during the synthesis of the procatalyst prior to or simultaneous with the addition of an internal donor
  • activating compound as used in the present description means: a compound used to activate the solid support prior to contacting it with the catalytic species
  • modifier or “Group 13- or transition metal modifier” as used in the present description means: a metal modifier comprising a metal selected from the metals of Group 13 of the lUPAC Periodic Table of elements and transition metals. Where in the description the terms metal modifier or metal-based modifier is used, Group 13- or transition metal modifier is meant.
  • catalyst as used in the present description have the same meaning: a component of a catalyst composition generally comprising a solid support, a transition metal-containing catalytic species and optionally one or more internal donor.
  • halide or “halogen” as used in the present description means: an ion selected from the group of: fluoride (F-), chloride (CI-), bromide (Br-) or iodide (I-).
  • Heteroatom as used in the present description means: an atom other than carbon or hydrogen. However, as used herein - unless specified otherwise, such as below, - when “one or more hetereoatoms” is used one or more of the following is meant: F, CI, Br, I , N , O, P, B, S or Si. Thus a heteroatom also includes halides.
  • hydrocarbyl as used in the present description means: is a substituent containing hydrogen and carbon atoms, or linear, branched or cyclic saturated or unsaturated aliphatic radical, such as alkyl, alkenyl, alkadienyl and alkynyl; alicyclic radical, such as cycloalkyi, cycloalkadienyl cycloalkenyl; aromatic radical, such as monocyclic or polycyclic aromatic radical, as well as combinations thereof, such as alkaryl and aralkyl.
  • a hydrocarbyl group may be substituted with one or more non-hydrocarbyl substituent groups.
  • a non-limiting example of a non-hydrocarbyl substituent is a heteroatom.
  • alkoxycarbonyl viz. carboxylate
  • hydrocarbyl hydrocarbyl
  • alkyl as used in the present description means: an alkyl group being a functional group or side-chain consisting of carbon and hydrogen atoms having only single bonds.
  • An alkyl group may be straight or branched and may be un-substituted or substituted.
  • An alkyl group also encloses aralkyl groups wherein one or more hydrogen atoms of the alkyl group have been replaced by aryl groups.
  • aryl as used in the present description means: an aryl group being a functional group or side-chain derived from an aromatic ring. An aryl group and may be un-substituted or substituted with straight or branched hydrocarbyl groups. An aryl group also encloses alkaryl groups wherein one or more hydrogen atoms on the aromatic ring have been replaced by alkyl groups.
  • alkoxide or "alkoxy” as used in the present description means: a functional group or side- chain obtained from an alkyl alcohol. It consists of an alkyl bonded to a negatively charged oxygen atom.
  • aryloxide or "aryloxy” or “phenoxide” as used in the present description means: a functional group or side-chain obtained from an aryl alcohol. It consists of an aryl bonded to a negatively charged oxygen atom.
  • Grignard reagent or “Grignard compound” as used in the present description means: a compound or a mixture of compounds of formula R 4 z MgX 4 2-z (R 4 , z, and X 4 are as defined below) or it may be a complex having more Mg clusters, e.g. R4Mg3Cl2.
  • polymer as used in the present description means: a chemical compound comprising repeating structural units, wherein the structural units are monomers
  • alkene as used in the present description means: an alkene
  • olefin-based polymer or “polyolefin” as used in the present description means: a polymer of one or more alkenes.
  • propylene-based polymer as used in the present description means: a polymer of propylene and optionally a comonomer.
  • polypropylene as used in the present description means: a polymer of propylene
  • copolymer as used in the present description means: a polymer prepared from two or more different monomers.
  • “monomer” as used in the present description means: a chemical compound that can undergo polymerization.
  • MWD weight-average molecular weight
  • M n number average molecular weight
  • M w and M n are determined by GPC using a Waters 150 °C gel permeation chromatograph combined with a Viscotek 100 differential viscosimeter; the chromatograms were run at 140 °C using 1 ,2,4-trichlorobenzene as a solvent; the refractive index detector was used to collect the signal for molecular weights.
  • “bulk density” as used in the present description means: the weight per unit volume of a material, including voids inherent in the material as tested. Bulk density is measured as apparent density according to ASTM D1895-96 Reapproved 2010-e1 , test method A.
  • "XS" or “xylene soluble fraction” or “CXS” or “cold soluble xylene fraction” as used in the present description means: the weight percentage (wt.%) of soluble xylene in the isolated polymer, measured according to ASTM D 5492-10.
  • polymerization conditions means: temperature and pressure parameters within a polymerization reactor suitable for promoting polymerization between the catalyst composition and an olefin to form the desired polymer. These conditions depend on the type of polymerization used.
  • production rate or “yield” as used in the present description means: the amount of kilograms of polymer produced per gram of procatalyst consumed in the polymerization reactor per hour, unless stated otherwise.
  • MFR or “Melt Flow rate” as used in the present description is measured at a temperature of 230 °C with 2.16 kg load and measured according to ISO 1 133:2005.
  • any R group is "independently selected from” this means that when several of the same R groups are present in a molecule they may have the same meaning or they may not have the same meaning.
  • the present invention is described below in more detail. All embodiments described with respect to one aspect of the present invention are also applicable to the other aspects of the invention, unless otherwise stated.
  • An advantage of the present invention is that high catalyst productivity is obtained. Another advantage is the increased bulk density of the polyolefin obtained. Another advantage is a more narrow molecular weight distribution of the polyolefin that is obtained.. Another advantage is the increased Mn (low oligomers) and low xylene solubles of the polyolefin obtained. Hence enhanced product physical and mechanical properties are expected such as for fibres, injection molded products and films when such products are obtained using the present invention.
  • the first aspect of the invention relates to a multistep process comprising steps A), B), C) and D): viz. to a process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, said process comprising the steps of: Step A) providing or preparing a Grignard compound; Step B) contacting the Grignard compound an alkoxy- or aryloxy silane compound, to give a solid support; Step C) optionally contacting the solid support obtained with at least one activating compound; and Step D) reacting the (activated) support with a halogen-containing Ti-compound as catalytic species, an activator and at least one internal electron donor in several sub steps wherein the internal donor is added in portions during at least two of said stages to obtain a procatalyst.
  • the Ziegler-Natta type procatalyst in the catalyst system according to the present invention is obtained by the process that is similar to the process as described in EP202716B1 I.
  • Example I including all sub-examples (IA-IE) is incorporated into the present description. More details about the different embodiments are disclosed starting in paragraphs [0016] to [0089]. All these embodiments related to the process and products are incorporated by reference into the present description.
  • the process for preparing a procatalyst according to the present invention comprises the following phases or steps
  • phase I preparing a solid support for the procatalyst (Step A and Step B);
  • phase II optionally activating said solid support obtained in phase I using one or more activating compounds to obtain an activated solid support; (Step C);
  • phase III contacting said solid support obtained in phase I or said activated solid support in phase II with a catalytic species, an activator and at least one internal donor (Step D);
  • phase IV modifying said intermediate product obtained in phase III wherein phase IV may comprise one of the following: modifying said intermediate product obtained in phase III with a Group 13- or transition metal modifier in case an internal donor was used during phase III, in order to obtain a procatalyst; modifying said intermediate product obtained in phase III with a Group 13- or transition metal modifier and an internal donor in case an activator was used during phase III, in order to obtain a procatalyst.
  • the procatalyst thus prepared can be used in polymerization of olefins using e.g. an external electron donor and a co-catalyst.
  • the various steps used to prepare the catalyst according to the present invention are described in more detail below.
  • Phase I Preparing a solid support for the catalyst.
  • the process for preparing the solid support for the procatalyst according to the present invention comprises the following steps: step A) provision or preparation of a Grignard reagent; and Step B) reacting a Grignard compound with a silane compound.
  • Step A) may include the provision of a previously prepared or commercially obtained Grignard reagent or may include the preparation of a Grignard reagent.
  • Said Grignard reagent that is provided or prepared in step A is a compound R 4 z MgX 4 2-z.
  • R 4 is independently selected from linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms; preferably R 4 is phenyl or butyl, more preferably butyl.
  • X 4 is independently selected from the group consisting of fluoride (F-), chloride (CI-), bromide (Br-) or iodide (I-), preferably chloride, z is in a range of larger than 0 and smaller than 2, being 0 ⁇ z ⁇ 2.
  • Step A) including many embodiments, is described in detail in WO2015091984 A1 of the same applicant, page 15 line 14 to page 16, line 28, which complete section is incorporated here by reference.
  • Step B) includes contacting the compound R 4 z MgX 4 2- z (R 4 and X 4 being the same as above) with a silane compound Si(OR 5 ) 4-n (R 6 )n to give a first intermediate reaction product, being a solid Mg(OR 1 ) x X 1 2-x
  • R 1 , R 5 and R 6 are each independently selected from linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms
  • X 1 is independently selected from the group of consisting of fluoride (F-), chloride (CI-), bromide (Br-) or iodide (I-), preferably chloride
  • z is in a range of larger than
  • Step B) is described in detail in WO2015091984 A1 , page 16 line 30 to page 22, line 25, which complete section is incorporated here by reference.
  • a butyl Grignard is used during step A).
  • Phase II Activating said solid support for the catalyst (Step C).
  • This step of activating said solid support for the catalyst is an optional step that is not required, but is preferred, in the present invention.
  • This phase may comprise one or more stages.
  • Step C) relates to the activation of the solid magnesium compound and this step, including many embodiments, is described in detail in WO2015091984 A1 of the same applicant, page 23 line 3 to page 28, line 14, which complete section is incorporated here by reference.
  • the solid support and procatalyst preferably have an average particle size (or APS) of between 18 - 30 microns. The particle size is measured using a test method based on ASTM standard test method D4464-201 .
  • Step C) includes optionally contacting the solid support obtained in step B) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M 1 (OR 2 ) v -w(OR 3 ) w or M 2 (OR 2 ) v - w (R 3 )w, to obtain a second intermediate reaction product;
  • M 1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si
  • M 2 is a metal being Si
  • v is the valency of M 1 or M 2 and w ⁇ v, such as 0, 1 , or 2
  • R 2 and R 3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms,
  • activating electron donor an alcohol is used, such as methanol or ethanol, ethanol being more preferred.
  • TET titanium tetraethoxide
  • a combination of both an activating electron donor and a metal alkoxide compound is used, e.g. TET and ethanol.
  • step C) comprises an activation step with an activating electron donor and a metal alkoxide compound of formula M 1 (OR 2 ) v -w(OR 3 ) w , preferably methanol or ethanol, most preferred ethanol as activating electron donor and titanium tetraethoxide (TET) as metal alkoxide compound.
  • Ethanol is preferred over methanol in view of the toxicity of methanol.
  • Phase III preparing the procatalyst
  • Step D) involves reacting the first or second intermediate reaction product, obtained respectively in step B) or C), with a halogen-containing Ti-compound, an activator and at least one internal electron donor in several sub steps:
  • D-l in a first stage: contacting the first or second intermediate reaction product, obtained respectively in step B) or C), with a halogen-containing Ti-compound, an activator and optionally a portion of an internal electron donor;
  • step D-l I) in a second stage: contacting the product obtained in step D-l) with a halogen-containing Ti-compound, and optionally a portion of an internal electron donor;
  • step D-lll in a third stage: contacting the product obtained in step D-ll) with a halogen-containing Ti-compound, and optionally a portion of an internal electron donor;
  • step D-IV optionally in a fourth stage: contacting the product obtained in step D- III) with a halogen-containing Ti-compound, and optionally a portion of an internal electron donor;
  • said internal electron donor is added in at least two portions during at least two of the stages D-l, D-ll, D-lll, and D-IV to obtain said procatalyst.
  • phase III also called phase D
  • phase D is described in detail in WO2015091984 A1 of the same applicant, page 28 line 15 to page 31 , line 13, which complete section is incorporated here by reference.
  • Phase III may comprise several stages (e.g. I, II and III and optionally IV). During each of these consecutive stages the solid support is contacted with a catalytic species. In other words, the addition or reaction of said catalytic species may be repeated one or more times. Preferably, the same catalytic species is used each stage. Preferably TiCU is used as catalytic species in all stages of step D). The catalyst species may be added first followed by addition of an activator and/or donor in any of the stages.
  • Step D) involves, in all sub steps reacting the (activated) solid support with a transition metal halide (e.g. titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide) but preferably titanium halide, e.g. TiX 4 wherein X is chloride or fluoride, preferably chloride.
  • a transition metal halide e.g. titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide
  • TiX 4 wherein X is chloride or fluoride
  • the molar ratio of the activator relative to the magnesium may vary between wide limits, for instance from 0.02 to 1.0. Preferably, this molar ratio is from 0.05 to 0.8; more preferably from 0.1 to 0.6; and most preferably from 0.1 to 0.5. In an embodiment, an activator is present during this step D).
  • activators can be used, such as benzamide, alkylbenzoates, and monoesters. Each of these will be discussed below.
  • a benzamide activator has a structure as disclosed in WO2015091983 A1 of the same applicant, page 13, line 13- page 14, line 37, which complete section is incorporated here by reference.
  • a benzamide activator has a structure according to formula X:
  • R 70 and R 71 are each independently selected from hydrogen or an alkyl.
  • said alkyl has from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms. More preferably, R 70 and R 71 are each independently selected from hydrogen or methyl.
  • R 72 , R 73 , R 74 , R 75 , R 76 are each independently selected from hydrogen, a heteroatom (preferably a halide), or a hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof.
  • Said hydrocarbyl group may be linear, branched or cyclic.
  • Said hydrocarbyl group may be substituted or unsubstituted.
  • Said hydrocarbyl group may contain one or more heteroatoms.
  • said hydrocarbyl group has from 1 to 10 carbon atoms, more preferably from 1 to 8 carbon atoms, even more preferably from 1 to 6 carbon atoms.
  • benzamides include benzamide (R 70 and R 71 are both hydrogen and each of R 72 , R 73 , R 74 , R 75 , R 76 are hydrogen) also denoted as BA-2H or methylbenzamide (R 70 is hydrogen; R 71 is methyl and each of R 72 , R 73 , R 74 , R 75 , R 76 are hydrogen) also denoted as BA-HMe or dimethylbenzamide (R 70 and R 71 are methyl and each of R 72 , R 73 , R 74 , R 75 , R 76 are hydrogen) also denoted as BA-2Me.
  • Examples include monoethylbenzamide, diethylbenzamide, methylethylbenzamide, 2-(trifluor- methyl)benzamide, N,N-dimethyl-2-(trifluormethyl)benzamide, 3-(trifluormethyl)- benzamide, N,N-dimethyl-3-(trifluormethyl)benzamide, 2,4-dihydroxy-N-(2-hydroxyethyl)- benzamide, N-(1 /-/-benzotriazol-1 -ylmethyl)benzamide, 1 -(4-ethylbenzoyl)piperazine, 1 -benzoylpiperidine.
  • the present inventors believe that the fact that the most effective activation is obtained when the benzamide activator is added during stage I has the following reason. It is believed that the benzamide activator will bind the catalytic species and is later on substituted by the internal donor when the internal donor is added.
  • the activation is for example selected from the group consisting of butyl formate, ethyl acetate, amyl acetate, butyl acetate, ethyl acrylate, methyl methacrylate, isobutyl methacrylate, an alkyl benzoate, such as ethyl p-methoxy benzoate, methyl p-ethoxybenzoate, ethyl p- ethoxybenzoate, ethyl benzoate, methyl benzoate, propyl benzoate, ethyl p- chlorobenzoate, ethyl p-bromobenzoate, methyl-p-toluate and ethyl-naphthate; preferably ethyl acetate, ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, n-propyl benzoate, and benzoic anhydride, more
  • An internal electron donor is also present during step D). Also mixtures of internal electron donors can be used. Examples of internal electron donors are disclosed below.
  • the molar ratio of the internal electron donor relative to the magnesium may vary between wide limits, for instance from 0.01 to 0.75. Preferably, this molar ratio is from 0.02 to 0.5; more preferably from 0.03 to 0.3.
  • the internal donor may be added in one single portion during one of the stages I, II, III or IV.
  • the internal donor may also be added in split portions, e.g. in two portions or in three portions or even more. When the internal donor is added in two portions it may for example be added in Stage I and II or in stage II and III. When the internal donor is added in three portions, it may for example be added in stages I, II and III or in stages II, III and IV.
  • the internal electron donor is added in two portions wherein the amount of internal donor is split between these two portions in a weight ratio of from 80% : 20% to 20% : 80%, more preferably 60% : 40% to 40% : 60%, most preferably approximately 50% : 50%.
  • the internal electron donor is added in three portions wherein the amount of internal donor is split between these three portions in a weight ratio of from 20% to 40% for each portion, wherein the total of the three portions is 100%, most preferably each portion is between 30 to 35 % of the total amount of the internal donor.
  • R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are the same or different and are independently selected from a group consisting of hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof, preferably having from 1
  • N is a nitrogen atom
  • O is an oxygen atom
  • C is a carbon atom; preferably 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl ethyl carbamate (AB-OEt).
  • AB-OEt 4-[(ethoxycarbonyl)(methyl)amino]pentan-2-yl ethyl carbamate
  • the activator is added during stage I and the internal donor is added during stages II and III and optionally IV, preferably said activator being a monoester, and the internal donor being a carbonate-carbamate.
  • the activator EB is added during stage I and AB-OEt is added during stage II and stage III.
  • the activator EB is added during stage I and AB-OEt is added during stages II, III and IV.
  • EB is added as activator and wherein during stages II, III and IV, AB-OEt is added as internal donor in three portions, each portion having a weight ratio of from 30 to 35% wherein the total of the three portions equals 100%.
  • EB is added as activator and wherein during stages II and III, AB-OEt is added as internal donor in two portions, each portion having a weight ratio of from 60% : 40% to 40% : 60% wherein the total of the two portions equals 100%.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and Ethanol are used in step C), TiCU is used as catalytic species in all stages of step D); EB is used as activator in step D-l), AB-OEt is used as internal donor in stages II and III.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and Ethanol are first used in step C) and then ethanol is used in step C), TiCU is used as catalytic species in all stages of step D); EB is used as activator in step D-l), AB-OEt is used as internal donor in stages II and III.
  • butyl magnesium Grignard is used in step A
  • TES is used in step B
  • TET and Ethanol are used in step C
  • TiCU is used as catalytic species in all stages of step D
  • EB is used as activator in step D-l
  • AB-OEt is used as internal donor in stages II , III and IV.
  • each R 90 group is independently a substituted or unsubstituted aromatic group
  • R 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 are each independently the same or different and are independently selected from a group consisting of hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;.
  • N is nitrogen atom
  • O oxygen atom
  • C is carbon atom; preferably 4- [benzoyl(methyl)amino]pentan-2-yl benzoate (AB).
  • the activator is added during stage I and the internal donor is added during stage III. In an embodiment, the activator is added during stage I and the internal donor is added during stage II and III and optionally IV. Preferably said activator being a monoester, and the internal donor being an aminobenzoate.
  • the activator EB is added during stage I and AB is added during stage III. In a specific embodiment the activator EB is added during stage I and AB is added during stages II and III. In a specific embodiment the activator EB is added during stage I and AB is added during stages II and III and IV.
  • step I of step D EB is added as activator and wherein during stages II and III AB is added as internal donor in two portions, each portion having a weight ratio of from 60% : 40% to 40% : 60% wherein the total of the two portions equals 100%.
  • EB is added as activator and wherein during stages II, III and IV, AB is added as internal donor in three portions, each portion having a weight ratio of from 30 to 35% wherein the total of the three portions equals 100%.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and Ethanol are used in step C), TiCU is used as catalytic species in all stages of step D); EB is used as activator in step D-l), AB is used as internal donor in stages II and III.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and ethanol are first used in step C), TiCU is used as catalytic species in all stages of step D); EB is used as activator in step D-l), AB is used as internal donor in stage III.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and ethanol are used in step C), TiCU is used as catalytic species in all stages of step D); EB is used as activator in step D-l), AB is used as internal donor in stages II and III.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and Ethanol are first used in step C) and then ethanol is used in step C), TiCU is used as catalytic species in all stages of step D); EB is used as activator in step D-l), AB is used as internal donor in stages II, III and IV.
  • a 1 ,3-diether represented by the Formula C is used:
  • R 51 and R 52 are each independently selected from a hydrogen or a hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, and wherein R 53 and R 54 are each independently a hydrocarbyl group, selected from e.g. alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof.
  • Said hydrocarbyl group of R 53 -R 54 may be linear, branched or cyclic; it may be substituted or unsubstituted; it may contain one or more heteroatoms; it may have from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, more preferably from 1 -6 carbon atom, preferably 9,9- bis(methoxymethyl)fluorene (Flu). More information about this internal electron donor an several embodiments can be found in in WO2015/091983 which is incorporated by reference into the present application.
  • the activator is added during stage I and the internal donor is added during stage I, preferably said activator being a benzamide, and the internal donor being a 1 ,3-diether.
  • the activator BA-2Me is added during stage I and Flu is added during stage I.
  • the activator is added during stage I and the internal donor is added during stages I and II, preferably said activator being a benzamide, and the internal donor being a 1 ,3-diether.
  • the activator BA-2Me is added during stage I and Flu is added during stage I and stage II.
  • BA-2Me is added as activator and wherein during stages I and II Flu is added as internal donor in two portions, each portion having a weight ratio of from 60% : 40% to 40% : 60% wherein the total of the two portions equals 100% .
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and Ethanol are used in step C), TiCU is used as catalytic species in all stages of step D); BA-2Me is used as activator in step D-l), Flu is used as internal donor in stages I and II.
  • butyl magnesium Grignard is used in step A), TES is used in step B), TET and ethanol are first used in step C),TiCl4 is used as catalytic species in all stages of step D); BA-2Me is used as activator in step D-l), Flu is used as internal donor in stages I and II.
  • the catalyst system according to the present invention includes a co-catalyst.
  • a co-catalyst is a term well-known in the art in the field of Ziegler-Natta catalysts and is recognized to be a substance capable of converting the procatalyst to an active polymerization catalyst.
  • the co-catalyst is an organometallic compound containing a metal from group 1 , 2, 12 or 13 of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989- 1990).
  • the co- catalyst may include any compounds known in the art to be used as "co-catalysts", as described in WO2015091984 A1 of the same applicant, page 59 line 1 to page 60 line 30, which is incorporated here by reference.
  • External electron donor
  • the catalyst system according to the present invention preferably comprises an external electron donor.
  • an external donor compound is to affect the stereoselectivity of the catalyst system in polymerization of olefins having three or more carbon atoms. Therefore it may be also referred to as a selectivity control agent.
  • external donors suitable for use in the present invention are the internal donors benzoic acid esters and 1 ,3-diethers.
  • the following external donors may be used: alkylamino-alkoxysilanes, alkyl-alkoxysilane, imidosilanes, and alkylimidosilanes.
  • the aluminum/external donor molar ratio in the polymerization catalyst system preferably is from 0.1 to 200; more preferably from 1 to 100.
  • Mixtures of external donors may be present and may include from about 0.1 mol.% to about 99.9 mol.% of a first external donor and from about 99.9 mol.% to about 0.1 mol.% of either a second or the additional alkoxysilane external donor disclosed below.
  • the Si/Ti molar ratio in the catalyst system can range from 0.1 to 80, preferably from 0.1 to 60, even more preferably from 1 to 50 and most preferably from 2 to 30.
  • Patents EP1538167 and EP1783145 disclose a Ziegler-Natta catalyst type comprising an organo-silicon compound as external donor that is represented by formula Si(OR c )3(NR d R e ), wherein R c is a hydrocarbon group having 1 to 6 carbon atoms, R d is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen atom, and R e is a hydrocarbon group having 1 to 12 carbon atoms used as an external electron donor.
  • Suitable external donors according to the present invention are known from WO2015091984 A1 , being compounds according to Formula III, alkyl-alkoxysilanes according to Formula IV, organosilicon compounds having formula Si(OR a )4- n R b n, imidosilanes according to Formula I, alkylimidosilanes according to Formula ⁇ as described on page 61 line 26 to page 67 line 8 which is incorporated here by reference.
  • Alkoxy silane halide are used for preparing imidosilane and alkylimidosilane internal donors and are, respectively, according to Formula XXIVa: Z n Si(OR 1 1 )4-n and Formula XXIVa: Z n Si(OR 1 1 )4-n-m(R 12 )m.
  • the silane-compound for the additional external donor is dicyclopentyl dimethoxysilane, di-isopropyl dimethoxysilane, di-isobutyl dimethyoxysilane, methylcyclohexyl dimethoxysilane, n-propyl trimethoxysilane, n-propyltriethoxysilane, dimethylamino triethoxysilane, and one or more combinations thereof.
  • the external donor is an alkyl-alkoxysilane according to formula IV (preferably n-propyl trimethoxysilane or n-propyl triethoxysilane) or cyclohexylmethyldimethoxysilane or another dialkyldialkoxysilane.
  • the contacting temperature is between -30 °C to 120 °C, or between 0 °C and 100 °C, or between 10 °C and 60 °C; and contacting duration is between 10 to 150 minutes, or between 40 and 100 minutes.
  • stage D-l I the obtained reaction mixture is mixed at a temperature of between 60 °C and 140 °C, or between 90 °C and 120 °C for a period of between 10 to 150 minutes, or between 40 and 100 minutes; in stage D-lll) the obtained reaction mixture is mixed at a temperature of between 60 °C and 140 °C, or between 90 °C and 120 °C for a period of between 10 to 150 minutes, or between 20 and 80 minutes; in stage D-IV) the obtained reaction mixture is mixed at a temperature of between 60 °C and 140 °C, or between 90 °C and 120 °C for a period of between 10 to 150 minutes, or between 20 and 80 minutes; in stage D-IV) the obtained reaction mixture is mixed at a temperature of between 60 °C and 140 °C, or between 90 °C and 120 °C for a period of between 10 to 150 minutes,
  • the invention relates to a process for the preparation of a procatalyst suitable for preparing a catalyst composition for olefin polymerization, said process comprising the steps of:
  • Step C) optionally contacting the solid support obtained in step B) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M 1 (OR 2 ) v -w(OR 3 ) w or M 2 (OR 2 ) v - w (R 3 )w, to obtain a second intermediate reaction product; wherein M 1 , M 2 ; R 2 R 3 , and v and w are as discussed above;
  • Step D) reacting the first or second intermediate reaction product, obtained respectively in step B) or C), with a halogen-containing Ti-compound, an activator and at least one internal electron donor in several sub steps:
  • step D-l I) in a second stage: contacting the product obtained in step D-l) with a halogen-containing Ti-compound, and optionally an internal electron donor and mixing the obtained reaction mixture at a temperature of between 60 °C and 140 °C, preferably between 90 °C and 120 °C for a period of between 10 to 150 minutes, preferably between 40 and 100 minutes;
  • step D-lll in a third stage: contacting the product obtained in step D-ll) with a halogen-containing Ti-compound, and optionally an internal electron donor and mixing the obtained reaction mixture at a temperature of between 60 °C and 140 °C, preferably between 90 °C and 120 °C for a period of between 10 to 150 minutes, preferably between 20 and 80 minutes;
  • step D-IV optionally in a fourth stage: contacting the product obtained in step D-lll) with a halogen-containing Ti-compound, and optionally an internal electron donor and mixing the obtained reaction mixture at a temperature of between 60 °C and 140 °C, preferably between 90 °C and 120 °C for a period of between 10 to 150 minutes, preferably between 20 and 80 minutes;
  • the temperature of addition of the components during Stage I of step D) is between 0 and 40 °C, such as between 20 and 30 °C, for example 25 °C.
  • the mixture of Stage I of Step D is mixed at the addition temperature for a period of between 10 to 150 minutes, preferably between 20 and 100 minutes, such as between 40 and 90 minutes, such as 60 minutes prior to increasing the temperature.
  • Step D during stage I the addition is carried out at a temperature of between 20 and 30 °C and then mixed for a period of between 40 and 90 minutes, the temperature is then raised to between 90 and 120 °C and then mixed for a period of between 40 and 90 minutes; stage II the components are added and at a temperature between 90 and 120 °C and then mixed for a period of between 40 and 80 minutes; stage III the components are added and at a temperature between 90 and 120 °C and then mixed for a period of between 20 and 60 minutes; stage IV the components are added and at a temperature between 90 and 120 °C and then mixed for a period of between 20 and 60 minutes.
  • stage I is carried out with BA-2Me added at a temperature of 25 °C and heated to a reaction temperature of 1 15 °C and a stirring time of 60 minutes; stage II is carried out at 1 15 °C for 60 minutes, stage III at 1 15 °C for 60 minutes and stage IV at 1 15 °C for 30 minutes.
  • stage I is carried out with BA-2Me added at a temperature of 25 °C and heated to a reaction temperature of 1 15 °C and a stirring time of 60 minutes; stage II is carried out at 105 °C for 60 minutes, stage III at 105 °C for 30 minutes and stage IV at 105 °C for 60 minutes.
  • stage I is carried out with EB added at temperature of 25 °C and heated to a reaction temperature of 1 15 °C and a stirring time of 90 minutes; stage II is carried out at 1 15 °C for 60 minutes, stage III at 1 15 °C for 30 minutes and stage IV at 1 15 °C for 30 minutes.
  • stage I is carried out with EB added at a temperature of 25 °C and heated to a reaction temperature of 1 15 °C and a stirring time of 90 minutes; stage II is carried out at 1 15 °C for 60 minutes, stage III at 1 15 °C for 30 minutes and stage IV at 1 15 °C for 30 minutes.
  • step ii) is carried out using ethanol as activating electron donor.
  • step ii) is carried out using an activating electron donor and a metal alkoxide compound of formula M 1 (OR 2 ) v -w(OR 3 ) w during step ii), preferably ethanol as activating electron donor and titanium tetraethoxide (TET) as metal alkoxide compound.
  • the internal donor is added in at least two of the stages of step D, or in three stages of step D.
  • the invention also relates to a process to make the catalyst system by contacting a Ziegler-Natta type procatalyst, a co-catalyst and optionally one or more external electron donors.
  • the procatalyst, the co-catalyst and the external donor(s) can be contacted in any way known to the skilled person in the art; and as also described herein, more specifically as in the Examples.
  • the invention further relates to a process of preparing a polyolefin by contacting at least one olefin with a polymerization catalyst system comprising the procatalyst according to the present invention.
  • the polyolefin made by using the catalyst system of the present invention is a polypropylene.
  • the external donor in the catalyst system according to the present invention can be complexed with the co-catalyst and mixed with the procatalyst (pre-mix) prior to contact between the procatalyst and the olefin.
  • the external donor can also be added independently to the polymerization reactor.
  • the procatalyst, the co-catalyst, and the external donor can be mixed or otherwise combined prior to addition to the polymerization reactor.
  • Contacting the olefin with the catalyst system according to the present invention can be done under standard polymerization conditions, known to the skilled person in the art. See for example Pasquini, N. (ed.) "Polypropylene handbook” 2 nd edition, Carl Hanser Verlag Kunststoff, 2005. Chapter 6.2 and references cited therein. Polymerization process
  • the polymerization process may be a gas phase, a slurry or a bulk polymerization process, operating in one or more than one reactor.
  • One or more olefin monomers can be introduced in a polymerization reactor to react with the procatalyst and to form an olefin- based polymer (or a fluidized bed or agitated bed of polymer particles).
  • the olefin according to the invention may be selected from mono- and di-olefins containing from 2 to 40 carbon atoms; see also WO2015091984 A1 of the same applicant, page 72 line 28 to page 73 line 5 which section is incorporated here by reference.
  • the olefin is propylene or a mixture of propylene and ethylene, to result in a propylene-based polymer, such as propylene homopolymer or propylene-olefin copolymer.
  • the olefin may an alpha-olefin having up to 10 carbon atoms, such as ethylene, butene, hexene, heptene, octene.
  • the present invention also relates to a polyolefin, preferably a polypropylene obtained or obtainable by a process, comprising contacting an olefin, preferably propylene or a mixture of propylene and ethylene with the procatalyst according to the present invention. More information about the polymers formed is disclosed WO2015091984 A1 of the same applicant, page 73 lines 6-23 and 25-34 and page 74 line 26 page 75, line 24 which section is incorporated by reference entirely.
  • the present invention also relates to a polyolefin, preferably a propylene-based polymer obtained or obtainable by a process as described herein above, comprising contacting propylene or a mixture of propylene and ethylene with a catalyst system according to the present invention.
  • the present invention relates to the production of a homopolymer of polypropylene.
  • Xylene soluble fraction (XS) is preferably from about 0.5 wt% to about 10 wt%, or from about 0.5 wt% to about 8 wt%, or from 1 .0 to 6 wt%.
  • the production rate is preferably from about 1 kg/g/hr to about 100 kg/g/hr, or from about 20 kg/g/hr to about 90 kg/g/hr.
  • MFR is preferably from about 0.01 g/10 min to about 2000 g/10 min, or from about 0.01 g/10 min to about 1000 g/10 min; or from about 0.1 g/10 min to about 500 g/10 min, or from about 0.5 g/10 min to about 150 g/10 min, or from about 1 g/ 10 min to about 100 g/10 min.
  • the invention also relates to the use of the polyolefins, preferably the propylene-based polymers (also called polypropylenes) according to the invention in injection moulding, blow moulding, extrusion moulding, compression moulding, casting, thin-walled injection moulding, etc. for example in food contact applications.
  • the invention relates to a shaped article comprising the polyolefin, preferably the propylene-based polymer according to the present invention.
  • the polyolefin, preferably the propylene-based polymer according to the present invention may be transformed into shaped (semifinished articles using a variety of processing techniques. Examples of suitable processing techniques include injection moulding, injection compression moulding, thin wall injection moulding, extrusion, and extrusion compression moulding.
  • Injection moulding is widely used to produce articles such as for example caps and closures, batteries, pails, containers, automotive exterior parts like bumpers, automotive interior parts like instrument panels, or automotive parts under the bonnet. Extrusion is for example widely used to produce articles, such as rods, sheets, films and pipes. Thin wall injection moulding may for example be used to make thin wall packaging applications both for food and non-food segments. This includes pails and containers and yellow fats/margarine tubs and dairy cups.
  • Example 1 fnot according to first aspect of invention; according to second aspect of invention!
  • reaction product of step A 500 ml, 0.45 mol Mg
  • 260 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE), 47 ml of TES and 213 ml of DBE
  • TES tetraethoxysilane
  • DBE dibutyl ether
  • the minimixer was cooled to 5°C by means of cold water circulating in the minimixer's jacket.
  • the stirring speed in the minimixer was 1000 rpm.
  • the solid product obtained was washed five times with 125 ml of heptane starting at 60°C with 5 minutes stirring per wash prior to filtration. The temperature was gradually reduced from 60 to 25°C during the washings. Finally, the solid product obtained was dried using a nitrogen purge at a temperature of 25°C for 2 hours.
  • the composition of the solid procatalyst A produced is given in Table 1.
  • Example 2 Tnot according to first aspect of invention; according to second aspect of invention!
  • Example 2 was carried out in the same way as Example 1 , except that stages II, III and IV of procatalyst preparation were carried out at 105°C instead of 1 15°C.
  • the composition of the solid procatalyst B produced is given in Table 1.
  • Example 3 Taccording to first aspect of invention; according to second aspect of invention]
  • Steps A-C are carried out in the same way as in Example 1 .
  • Step D) was carried out as follows.
  • BA-2Me/Mg 0.15 molar ratio
  • the solid product obtained was washed five times with 125 ml of heptane starting at 60°C with 5 minutes stirring per wash prior to filtration. The temperature was gradually reduced from 60 to 25°C during the washings. Finally, the solid product obtained was dried using a nitrogen purge at a temperature of 25°C for 2 hours.
  • the composition of the solid procatalyst C produced is given in Table 1.
  • Example 4 was carried out in the same way as Example 3, except that in stage I of procatalyst preparation 0.7 g instead of 0.5 g of 9,9-bis-methoxymethyl-9H-fluorene was used and in II stage of procatalyst preparation 0.7 g instead of 0.5 g of 9,9-bis- methoxymethyl-9H-fluorene was used.
  • the composition of the solid procatalyst D produced is given in Table 1 .
  • Steps A-C are carried out as in Example 1 .
  • Step D) was carried out as follows:
  • EB ethylbenzoate
  • the solid product obtained was washed five times with 125 ml of heptane starting at 60°C with 5 minutes stirring per wash prior to filtration. The temperature was gradually reduced from 60 to 25°C during the washings. Finally, the solid product obtained was dried using a nitrogen purge at a temperature of 25°C for 2 hours.
  • the composition of the solid procatalyst E produced is given in Table 1.
  • Steps A-C are carried out as in Example 1 .
  • Step D) was carried out as follows:
  • EB ethylbenzoate
  • Example 7 Tnot according to first aspect of invention; not according to second aspect of invention!
  • This step was carried out as described in Example XX of EP 1 222 214 B1 , except that the dosing temperature of the reactor was 35 °C, the dosing time was 360 min and a stirrer was used. 250 ml of dibutyl ether was introduced to a 1 liter reactor. The reactor was thermostated at 35 °C.
  • reaction mixture was heated up to 60°C and kept at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting. The solid substance was washed three times using 500 ml of heptane. As a result, a pale yellow solid substance, reaction product B (the solid first intermediate reaction product; the support), was obtained, suspended in 200 ml of heptane.
  • a 250 mL reactor is brought under nitrogen and 125 ml of titanium tetrachloride is added to it.
  • the reactor is heated to 90°C under stirring and a suspension, containing about 5.5 g of activated support in 15 ml of heptane, is added to it under stirring.
  • the reaction mixture was kept at 90°C for 60 min.
  • the solid is allowed to settle and is washed with 125 ml chlorobenzene at 90°C for 15-20 min.
  • the solid is allowed to settle and decanted.
  • the solid substance obtained is washed five times using 100-150 ml of heptane at 60°C, after which the procatalyst, suspended in heptane, is obtained.
  • the composition of the solid procatalyst G produced is given in Table 1 .
  • Steps ⁇ '), B') and C) were carried out as in Example 7.
  • Step D') is carried out as follows.
  • a reactor was brought under nitrogen and 125 ml of titanium tetrachloride was added to it.
  • EB/Mg molar ratio 0.3
  • the solid substance obtained was washed five times using 150 ml of heptane at 60°C, after which the procatalyst, suspended in heptane, was obtained.
  • composition of the solid procatalyst H produced is given in Table 1.
  • Liquid pool propylene polymerization was carried out in a one gallon bench scale reactor.
  • the method of polymerization involved baking the polymerization reactor at 1 10°C for 60 min, applying three high pressure (15 bar) nitrogen purges at 1 10°C, then lowering the reactor temperature to 30°C whilst purging the reactor with nitrogen. Then the reactor was purged three times, with 50 g of propylene for each purge. Then, 1 .375 kg of liquid propylene was introduced to the reactor followed by the addition of 200 psig hydrogen to the reactor from an 75 mL stainless steel cylinder. The reactor temperature was then raised to 62°C, and stirring speed set to 500 rpm.
  • Example 7 which is a comparative example.
  • the catalyst productivity is more than doubled from 12.4 to a value between 24.5 and 27.0.
  • the bulk density is increased from 326 to a value between 369 and 395.
  • the MWD is lowered from 6.63 to a value between 4.20 and 5.40.
  • the Mn is doubled from 29176 to a value between 54000 and 65878, hence there are less oligomers.
  • One or more aims are therefore achieved by the present invention: being high catalyst productivity, high bulk density, narrow molecular weight distribution, increased Mn (low oligomers) and low xylene solubles.
  • Example 1 Enhanced product physical and mechanical properties are expected such as for fibres, injection molded products and films with such products.
  • Example 7 comparative
  • a low temperature of addition of the reagents in Stage I of step D 25 °C for Example 1 versus 90 °C for Example 7
  • a longer stirring duration of Stage I I of step D 60 minutes for Examplel versus 30 minutes for Example 7 leads to a doubling in the productivity (from 12.4 to 24.6), an increase in bulk density (from 326 to 371 ), an increase in Mw and Mn and a decrease in MWD (from 6.63 to 4.40).
  • Example 5 When Example 5 is compared to Example 8 it is clear that a low temperature of addition of the reagents in Stage I of step D (25 °C for Example 5 versus 100 °C for Example 8) as well as a longer stirring duration of Stage I of step D (90 minutes for Example 5 versus 60 minutes for Example 8) leads to an increase in the productivity (from 17.3 to 21 .2), an increase in Mn (lower oligomers) and narrower MWD (from 6.63 to 5.00) as well as lower XS (from 3.34 to 2.87).
  • temperature during the process can surprisingly be used to control product parameters, such as Ml, MWD and XS. It is noted that the temperature in stages II, III and IV is decreased from 1 15 °C in Example 1 to 105 °C in Example 2. This is results in the following.
  • the MWD is higher (5.4 compared to 4.4); the Ml is higher (13.9 compared to 10.6); and the XS is lower (2.85 compared to 3.1 1 ).
  • the split (e.g. double or triple) addition of internal donor improves the incorporation of the internal donor in the catalyst from, which represents a significant saving on donor utilization. It increases the productivity, bulk density, Ml and decreases XS. Also, surprisingly the Mn is higher (lower oligomers) with split addition of the internal donor.
  • Example 3 half of Flu in stage I and half of Flu in stage II
  • Example 1 all Flu in stage I, total amount the same
  • the productivity is higher (27.0 compared to 24.6); the bulk density is higher (395 compared to 371 ); the Ml is higher (13.3 compared to 10.9); and XS is lower (2.07 compared to 3.1 1 ).
  • the split addition increases the incorporation of the Flu in the catalyst from 15.45 % to 17.7 %.
  • Example 6 triple addition of AB-OEt
  • Example 5 double addition of AB-OEt
  • the productivity is somewhat higher (22.5 compared to 21.2); the Ml is higher (2.92 compared to 2.09); the MWD is lower (4.65 compared to 5.00)
  • the procatalyst in this disclosure was found to produce high procatalyst productivity, high bulk density, narrow molecular weight distribution, increased Mn (low oligomers) and low xylene solubles.
  • Enhanced product physical and mechanical properties are expected such as for fibres, injection molded products and films with such products. Hence one or more objects of the present invention have been obtained.
EP17730197.5A 2016-09-29 2017-06-19 Verfahren zur herstellung eines prokatalysators zur polymerisierung von olefinen Pending EP3519457A1 (de)

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US10882929B2 (en) 2016-09-29 2021-01-05 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
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CN109843944B (zh) 2016-09-29 2022-02-22 Sabic环球技术有限责任公司 用于制备用于烯烃聚合的主催化剂的方法
US11254757B2 (en) 2016-10-12 2022-02-22 Sabic Global Technologies B.V. Process to prepare a solid support for a procatalyst suitable for polymerization of olefins
EP4061527A1 (de) * 2019-11-22 2022-09-28 SABIC Global Technologies B.V. Verfahren zum herstellen eines prokatalysators zur polymerisation von olefinen

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4946816A (en) 1989-08-21 1990-08-07 Amoco Corporation Morphology-controlled olefin polymerization catalyst
JP3304462B2 (ja) 1993-01-04 2002-07-22 住友化学工業株式会社 エチレン−プロピレンブロック共重合体の製造方法
WO1996032426A1 (en) 1995-04-10 1996-10-17 Dsm N.V. Method for the preparation of a catalyst suitable for the polymerisation of an olefine
US6780808B2 (en) 2002-07-15 2004-08-24 Univation Technologies, Llc Enhanced solubility of magnesium halides and catalysts and polymerization process using same
AU2003257555A1 (en) 2002-08-19 2004-03-03 Ube Industries, Ltd. CATALYSTS FOR POLYMERIZATION OR COPOLYMERIZATION OF Alpha-OLEFINS, CATALYST COMPONENTS THEREOF, AND PROCESSES FOR POLYMERIZATION OF Alpha-OLEFINS WITH THE CATALYSTS
WO2006011334A1 (ja) 2004-07-28 2006-02-02 Mitsui Chemicals, Inc. オレフィン重合用触媒及び該触媒を用いる重合方法
EA013392B1 (ru) 2006-05-24 2010-04-30 Сауди Бейсик Индастриз Корпорейшн Способ получения каталитического компонента для полимеризации пропилена
US8288585B2 (en) 2008-12-31 2012-10-16 Dow Global Technologies Llc Procatalyst composition with substitute 1,2-phenylene aromatic diester internal donor and method
KR101874650B1 (ko) 2010-02-26 2018-07-04 더블유.알. 그레이스 앤드 캄파니-콘. 치환된 아미드 에스테르 내부 전자 공여체를 갖는 전촉매 조성물
JP2011246698A (ja) * 2010-04-28 2011-12-08 Sumitomo Chemical Co Ltd オレフィン重合用固体触媒成分の製造方法
US20120157295A1 (en) 2010-12-21 2012-06-21 Linfeng Chen Process for Producing Procatalyst Composition with Alkoxyalkyl Ester Internal Electron Donor and Product
CN104204001A (zh) * 2012-02-22 2014-12-10 沙特基础工业公司 用于烯烃聚合的催化剂组分
JP6285425B2 (ja) 2012-06-29 2018-02-28 サウディ ベーシック インダストリーズ コーポレイション オレフィン重合用触媒組成物
KR102060850B1 (ko) * 2013-02-27 2020-02-11 도호 티타늄 가부시키가이샤 올레핀류 중합용 고체 촉매 성분의 제조 방법, 올레핀류 중합용 촉매 및 올레핀류 중합체의 제조 방법
CN105934449B (zh) * 2013-12-20 2018-07-10 沙特基础工业公司 用于烯烃聚合的催化剂组合物
MX2016008041A (es) * 2013-12-20 2017-03-03 Saudi Basic Ind Corp Sistema catalizador para polimerizacion de una olefina.
EA028922B1 (ru) * 2013-12-20 2018-01-31 Сауди Бейсик Индастриз Корпорейшн Прокатализатор для полимеризации олефинов
KR20170015386A (ko) 2014-06-02 2017-02-08 사빅 글로벌 테크놀러지스 비.브이. 올레핀 중합용 주촉매
CN106414520A (zh) 2014-06-02 2017-02-15 Sabic环球技术有限责任公司 用于烯烃聚合的包含单酯和氨基苯甲酸酯内部供体的原催化剂
WO2015193291A1 (en) 2014-06-20 2015-12-23 Sabic Global Technologies B.V. Process for the polymerization of propylene
CN109843944B (zh) 2016-09-29 2022-02-22 Sabic环球技术有限责任公司 用于制备用于烯烃聚合的主催化剂的方法
EP3519459B1 (de) 2016-09-29 2023-10-11 SABIC Global Technologies B.V. Katalysator zur polymerisation von olefinen
US10882929B2 (en) 2016-09-29 2021-01-05 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
US11254757B2 (en) 2016-10-12 2022-02-22 Sabic Global Technologies B.V. Process to prepare a solid support for a procatalyst suitable for polymerization of olefins

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